A silicone glass silicone resin, and a preparation method and application thereof

Abstract

The application provides an organic silicon glass silicon resin, a preparation method and application thereof, and raw materials of the organic silicon glass silicon resin include the following components in terms of weight parts: spherical silicon resin 100 parts; crosslinking agent 1-5 parts; catalyst 0.5-5 parts; tackifier 0.1-2 parts; cellusolve 1-10 parts; leveling agent 1-10 parts. The organic silicon glass silicon resin provided by the application meets the requirements of lens spraying protection in various performances, has high hardness, the surface of the cured glue is very smooth, has excellent anti-friction performance, and can play a good protective role on various substrates by coating a very thin layer.

Description

Technical Field

[0001] The present invention belongs to the technical field of silicone resins, and relates to an organic silicon glass silicone resin and a preparation method and application thereof, and in particular to an organic silicon glass silicone resin specially used for high-hardness and friction-resistant glass lenses and a preparation method thereof. Background Art

[0002] Epoxy resins, polyester resins, and phenolic resins are commonly used in the market today, but they all suffer from drawbacks such as poor light transmittance, thick films, flammability when exposed to open flames, and the generation of heavy smoke. Furthermore, they have high viscosity and poor permeability, failing to meet the requirements for thin films, high hardness, high light transmittance, high adhesion, chemical resistance, and high and low-temperature resistance. With the continued expansion of applications for translucent lenses, aircraft flight covers, various glass, ceramics, various artificial boards, various resins (ABS, PC, PP, acrylic, plexiglass), various precious wood products, various ferrous and non-ferrous metal products (titanium-magnesium alloys, titanium alloys, stainless steel, copper, aluminum, and electroplated metal products), automotive exterior paint protection films, and electronic products, improving the service life and stability of these materials has become an increasingly important issue. While applying a highly transparent hard protective film to the surfaces of lenses, glass, aircraft covers, and the like can effectively extend their service life, the hardness and wear resistance of existing protective films remain to be further improved. Summary of the Invention

[0003] In response to the shortcomings of the prior art, the present invention provides an organosilicon glass silicone resin, its preparation method, and its application. The organosilicon glass silicone resin provided by the present invention not only meets the requirements for lens coating protection, but also has a high pencil hardness. The cured coating surface is very smooth and exhibits excellent anti-friction properties. Even a thin coating on a substrate can provide excellent protection.

[0004] To achieve this object, the present invention adopts the following technical solutions:

[0005] In a first aspect, the present invention provides an organosilicon glass silicone resin, wherein the raw materials for preparing the organosilicon glass silicone resin include the following components in parts by weight:

[0006]

[0007] The present invention uses silicone resin with a specific spherical MQ molecular structure as the main component to carry out alkoxy titanate catalytic grafting, and cooperates with tackifier, cellosolve and leveling agent components to achieve good chemical reaction. As a result, the prepared organic silicon glass silicone resin not only meets the requirements of lens spray protection in various properties, but also has high hardness. The surface of the cured adhesive is very smooth and has excellent anti-friction performance. It can play a good protective role by coating a very thin layer on the surface of various substrates.

[0008] The organosilicon glass silicone resin provided by the present invention exhibits excellent high and low temperature resistance, weather resistance, high hardness, can be dried to form a film at room temperature, has high light transmittance, and is easy to control. After room temperature curing, it can significantly improve the wear resistance, oil resistance, and chemical resistance of various materials, forming a dense, friction-resistant protective film on various surfaces. Even a thin coating can provide excellent protection on a variety of substrates, making it highly applicable in a wide range of applications.

[0009] In the present invention, the raw materials for preparing the organosilicon glass silicone resin are calculated in parts by weight, with the amount of spherical silicone resin being 100 parts by weight.

[0010] The amount of the cross-linking agent can be 1 part by weight, 2 parts by weight, 3 parts by weight, 4 parts by weight, 5 parts by weight, etc.;

[0011] The amount of the catalyst can be 0.5 parts by weight, 1 part by weight, 1.5 parts by weight, 2 parts by weight, 2.5 parts by weight, 3 parts by weight, 3.5 parts by weight, 4 parts by weight, 4.5 parts by weight, 5 parts by weight, etc.;

[0012] The amount of the tackifier can be 0.1 parts by weight, 0.5 parts by weight, 1 part by weight, 1.5 parts by weight, 2 parts by weight, etc.;

[0013] The amount of cellosolve can be 1 part by weight, 2 parts by weight, 3 parts by weight, 4 parts by weight, 5 parts by weight, 6 parts by weight, 7 parts by weight, 8 parts by weight, 9 parts by weight, 10 parts by weight, etc.

[0014] The amount of the leveling agent can be 1 part by weight, 2 parts by weight, 3 parts by weight, 4 parts by weight, 5 parts by weight, 6 parts by weight, 7 parts by weight, 8 parts by weight, 9 parts by weight, 10 parts by weight, etc.

[0015] Preferably, the spherical silicone resin has a structure shown in the following formula (I):

[0016] [(R 2 SiO 3 / 2 ] a [R 1 2SiO 2 / 2 ] b [SiO 4 / 2 ] c [(R 3 2R 2 SiO 1 / 2 ] d Formula (I)

[0017] Among them, R 1 =C2H5, R 2 =CH3, R 3=CH3O or C2H5O; a, b, c, d represent molar ratios and satisfy the following conditions: a is 0.65-0.9 (e.g., 0.65, 0.7, 0.8, 0.9, etc.), b is 0.01-0.05 (e.g., 0.01, 0.02, 0.03, 0.04, 0.05, etc.), c is 0.1-0.35 (e.g., 0.1, 0.2, 0.3, 0.35, etc.), d is 0.001-0.2 (e.g., 0.001, 0.005, 0.008, 0.01, 0.03, 0.05, 0.08, 0.1, 0.13, 0.15, 0.18, 0.2, etc.), and a+b+c=1;

[0018] The molar ratio of R to Si is 0.6 to 1.4 (e.g., 0.6, 0.8, 1, 1.2, 1.4, etc.), and R is R 1 、R 2 and R 3 The group represented.

[0019] Preferably, the spherical silicone resin is prepared by the following method:

[0020] (a) alkyl orthosilicate, alkyltrialkoxysilane, diethyldialkoxysilane and water are mixed, an acid catalyst is then added, the temperature is raised, hydrolyzed under agitation, and then reacted under reflux and stirring, a pH adjusting agent is then added, the mixture is allowed to stand, lower layer of waste water is drained off, and alcohol and water are then vacuum-desorbed to obtain a pre-polymerized concentrated silicone resin, and a reactive diluent is added to obtain a pre-polymerized concentrated silicone resin solution;

[0021] (b) adding an alkyltrialkoxysilane and a titanium catalyst to the pre-polymerized concentrated silicone resin solution obtained in step (a), reacting, then distilling off methanol, ethanol, and a reactive diluent to obtain the spherical silicone resin, and then adding a reactive diluent to obtain a spherical silicone resin solution.

[0022] The spherical silicone resin provided by the present invention has a spherical chemical structure. The organic silicon glass silicone resin prepared using it as the main component has a very dense structure and a very smooth surface after curing. It has high pencil hardness, excellent friction resistance, high adhesion to substrates, low-temperature resistance, excellent leveling properties, and high light transmittance. It can be used as a hardening coating for transparent plastics such as organic glass (PMMA), polycarbonate (PC), and polystyrene (PS), as well as wood and ceramics, to improve their wear resistance, corrosion resistance, and aging resistance, and can also improve the light transmittance of optical lenses made from these materials. It can also be used as a protective coating for various metal products and decorative materials, improving their wear resistance, aging resistance, water resistance, UV resistance, and corrosion resistance, and has very wide application value.

[0023] Preferably, the alkyl orthosilicate includes methyl orthosilicate and / or ethyl orthosilicate.

[0024] Preferably, the alkyltrialkoxysilane of step (a) and step (b) each independently comprises methyltrimethoxysilane and / or methyltriethoxysilane.

[0025] Preferably, the diethyldialkoxysilane of step (a) comprises diethyldiethoxysilane.

[0026] Preferably, the total moles of alkoxy groups in the alkyl orthosilicate, alkyltrialkoxysilane and diethyldialkoxysilane to the moles of water is in the range of 1 : (0.4-0.8), for example 0.4, 0.5, 0.6, 0.7, 0.8, etc.

[0027] Preferably, the molar ratio of the alkyl orthosilicate, alkyltrialkoxysilane, diethyldialkoxysilane is in the range of (0.1-0.35):(0.65-0.9):(0.01-0.05), for example 0.1, 0.2, 0.3, 0.35, etc. for the first component, 0.65, 0.7, 0.8, 0.9, etc. for the second component, and 0.01, 0.02, 0.03, 0.04, 0.05, etc. for the third component.

[0028] Preferably, the acid catalyst comprises any one or a combination of at least two of hydrochloric acid, acetic acid, formic acid, boric acid, nitric acid, sulfuric acid or triflic acid.

[0029] Preferably, the acid catalyst is added in an amount such that the pH of the system is in the range of 3-4, for example 3, 3.3, 3.5, 3.8, 4, etc.

[0030] Preferably, the temperature of step (a) is in the range of 40-75°C, for example 40°C, 45°C, 50°C, 55°C, 60°C, 65°C, 70°C, 75°C, etc.

[0031] Preferably, the time of hydrolysis of step (a) is in the range of 1-8h, for example 1h, 2h, 3h, 4h, 5h, 6h, 7h, 8h, etc.

[0032] Preferably, the temperature of the reaction of step (a) is in the range of 75-150°C, for example 75°C, 80°C, 90°C, 100°C, 110°C, 120°C, 130°C, 140°C, 150°C, etc., and the time of the reaction is in the range of 2-8h, for example 2h, 3h, 4h, 5h, 6h, 7h, 8h, etc.

[0033] Preferably, the pH adjuster comprises hexamethyldisilazane and / or a base.

[0034] Preferably, the amount of the pH regulator added is such that the pH value of the system is 5 to 6, for example, 5, 5.2, 5.4, 5.6, 5.8, 6, etc.

[0035] Preferably, the temperature for removing ethanol and water in step (a) is 40-120°C, for example, 40°C, 50°C, 60°C, 70°C, 80°C, 90°C, 100°C, 110°C, 120°C, etc.

[0036] Preferably, the pre-polymerized concentrated silicone resin has a structure shown in the following formula (II):

[0037] [R 2 SiO 3 / 2 ] a [(R 1 2SiO 2 / 2 ] b [SiO 4 / 2 ] c [HO 1 / 2 ] d

[0038] Among them, R 1 =C2H5, R 2 =CH3; a, b, c, d represent molar ratios and satisfy the following conditions: a is 0.65-0.9 (e.g., 0.65, 0.7, 0.8, 0.9, etc.), b is 0.01-0.05 (e.g., 0.01, 0.02, 0.03, 0.04, 0.05, etc.), c is 0.1-0.35 (e.g., 0.1, 0.2, 0.3, 0.35, etc.), d is 0.001-0.2 (e.g., 0.001, 0.005, 0.008, 0.01, 0.03, 0.05, 0.08, 0.1, 0.13, 0.15, 0.18, 0.2, etc.), and a+b+c=1;

[0039] The molar ratio of R to Si is 0.6 to 1.4 (e.g., 0.6, 0.8, 1, 1.2, 1.4, etc.), and R is R 1 and R 2 The group represented.

[0040] Preferably, the active diluent in step (a) and step (b) comprises any one of ethyl acetate, butyl acetate, aromatic hydrocarbon solvents, ketone solvents or alcohol solvents, or a combination of at least two thereof.

[0041] Preferably, the mass ratio of the pre-polymerized concentrated silicone resin to the reactive diluent in step (a) is 1:(0.8-1.2), for example, 1:0.8, 1:0.9, 1:1, 1:1.1, 1:1.2, etc.

[0042] Preferably, in step (b), the amount of the alkyltrialkoxysilane added is 0.5-5% by weight of the pre-polymerized concentrated silicone resin, for example, 0.5%, 1%, 2%, 3%, 4%, 5%, etc.

[0043] Preferably, the titanium catalyst includes tetrabutyl titanate, isopropyl titanate, tetraethyl titanate, organic alkoxy titanate chelate (trade name 726) or any one of organic titanium chelates or a combination of at least two thereof.

[0044] Preferably, the organic titanium chelate compound includes any one of tris(acetylacetonate)aluminum, bis(ethyl acetoacetate)monoacetylacetonate aluminum or diisopropoxybis(ethyl acetoacetate)titanium, or a combination of at least two thereof.

[0045] Preferably, in step (b), the amount of the titanium catalyst added is 1 to 5% by weight of the pre-polymerized concentrated silicone resin, for example, 1%, 2%, 3%, 4%, 5%, etc.

[0046] Preferably, the reaction temperature in step (b) is 70-100°C, for example, 70°C, 80°C, 90°C, 100°C, etc., and the reaction time is 2-6h, for example, 2h, 3h, 4h, 5h, 6h, etc.

[0047] Preferably, the mass ratio of the spherical silicone resin to the reactive diluent in step (b) is 1:(0.6-1.5), for example, 1:0.6, 1:0.7, 1:0.8, 1:0.9, 1:1, 1:1.1, 1:1.2, 1:1.3, 1:1.24, 1:1.5, etc.

[0048] Preferably, the reactive diluent includes any one of ethyl acetate, butyl acetate, aromatic hydrocarbon solvents, ketone solvents or alcohol solvents, or a combination of at least two thereof.

[0049] Preferably, the aromatic hydrocarbon solvent includes xylene and / or toluene.

[0050] Preferably, the ketone solvent includes cyclohexanone.

[0051] Preferably, the alcohol solvent includes anhydrous methanol and / or anhydrous ethanol.

[0052] Preferably, the crosslinking agent includes any one of methyltrimethoxysilane, vinyltrimethoxysilane, methyltriethoxysilane, vinyltriethoxysilane, tetramethoxysilane or tetraethoxysilane, or a combination of at least two thereof.

[0053] Preferably, the catalyst includes any one of tetrabutyl titanate, isopropyl titanate, tetraethyl titanate or titanate chelate, or a combination of at least two thereof.

[0054] Preferably, the adhesion promoter includes any one of γ-glycidoxypropyltrimethoxysilane, aminopropyltrimethoxysilane, aminopropyltriethoxysilane or γ-aminoethylaminopropyltrimethoxysilane, or a combination of at least two thereof.

[0055] Preferably, the cellosolve comprises diethylene glycol monoethyl ether acetate.

[0056] Preferably, the leveling agent comprises butanol.

[0057] In a second aspect, the present invention provides a method for preparing the organosilicon glass silicone resin as described in the first aspect, the preparation method comprising the following steps:

[0058] The spherical silicone resin in a prescribed amount is mixed with a cross-linking agent and a catalyst, and then a tackifier, a cellosolve and a leveling agent are added and mixed to obtain the organosilicon glass silicone resin.

[0059] Preferably, the spherical silicone resin is added in the form of a spherical silicone resin solution.

[0060] Preferably, the spherical silicone resin solution comprises spherical silicone resin and a reactive diluent.

[0061] Preferably, in the spherical silicone resin solution, based on 100 parts by weight of the spherical silicone resin, the weight of the reactive diluent is 20 to 300 parts by weight, for example, 20 parts by weight, 40 parts by weight, 60 parts by weight, 80 parts by weight, 100 parts by weight, 120 parts by weight, 140 parts by weight, 160 parts by weight, 180 parts by weight, 200 parts by weight, 220 parts by weight, 240 parts by weight, 260 parts by weight, 280 parts by weight, 300 parts by weight, etc.

[0062] In a third aspect, the present invention provides a use of the organosilicon glass silicone resin described in the first aspect in a glass lens.

[0063] Compared with the prior art, the present invention has at least the following beneficial effects:

[0064] The present invention uses silicone resin with a specific spherical MQ molecular structure as the main component to carry out alkoxy titanate catalytic grafting, and cooperates with tackifier, cellosolve and leveling agent components to achieve good chemical reaction. As a result, the prepared organic silicon glass silicone resin not only meets the requirements of lens spray protection in various properties, but also has high hardness. The surface of the cured adhesive is very smooth and has excellent anti-friction performance. It can play a good protective role by coating a very thin layer on the surface of various substrates.

[0065] The experimental results show that the organosilicon glass silicone resin provided by the present invention has a high light transmittance (up to 99%) and a specific gravity of 1.1±0.1 (g / cm 3 , 25±2℃), viscosity is 5mm 2 / s~20mm 2 / s, surface drying time is 6min to 10min., it has excellent pencil hardness (above 6H), excellent friction resistance (haze value is less than 0.8%), and circle adhesion is level 1. DETAILED DESCRIPTION

[0066] The technical solution of the present invention is further described below by way of specific embodiments. It should be understood by those skilled in the art that the embodiments are merely to help understand the present invention and should not be regarded as specific limitations of the present invention.

[0067] Example 1

[0068] In this embodiment, an organosilicon glass silicone resin is provided, and a preparation method thereof comprises the following steps:

[0069] (a) 450 g of ethyl orthosilicate, 2000 g of methyltriethoxysilane, 80 g of diethyldiethoxysilane, and 450 g of H2O were weighed and added to an enameled reactor, stirred and mixed, and then 0.20 g of concentrated hydrochloric acid was dropwise added. The mixture was then hydrolyzed with a stirrer and heated to 70°C for 4 h. The mixture was then refluxed and stirred at 120°C for 6 h to obtain a concentrated silanol prepolymer. The mixture in the reactor became a colorless, transparent, homogeneous phase. 0.88 g of hexamethyldisilazane was added dropwise to adjust the pH to 5.5. The mixture was allowed to stand and drain the lower layer of wastewater. The ethanol and water were then removed under vacuum at 75°C at -0.09 MPa to obtain 810 g of pre-polymerized concentrated silicone resin. After cooling, 810 g of ethanol was added to obtain a pre-polymerized concentrated silicone resin solution.

[0070] (b) 21.8 g of methyltrimethoxysilane and 16.4 g of tetrabutyl titanate were added to the pre-polymerized concentrated silicone resin solution obtained in step (a) for grafting, and the mixture was stirred and reacted at 85° C. for 4 h. After the reaction was completed, excess methanol and ethanol were evaporated to obtain 815 g of the spherical silicone resin, and then 815 g of ethanol was added to obtain a spherical silicone resin solution.

[0071] In the spherical silicone resin obtained in this example, R / Si=0.878.

[0072] Take 200 g of the spherical silicone resin solution obtained above, add 2.8 g of methyltrimethoxysilane and 2.1 g of tetrabutyl titanate, 1 g of γ-aminoethylaminopropyltrimethoxysilane, 5 g of diethylene glycol monoethyl ether acetate, and 5 g of butanol, stir and mix evenly, then fill with nitrogen and store in a sealed manner to obtain the organic silicon glass silicone resin.

[0073] Example 2

[0074] In this embodiment, an organosilicon glass silicone resin is provided, and a preparation method thereof comprises the following steps:

[0075] (a) 450 g of methyl orthosilicate, 2200 g of methyltrimethoxysilane, 100 g of diethyldiethoxysilane, and 640 g of H2O were weighed and added to an enameled reactor, stirred and mixed, and then 0.256 g of concentrated hydrochloric acid was added dropwise. The mixture was then hydrolyzed with a stirrer and heated to 70°C for 4 h. The mixture was then refluxed and stirred at 120°C for 6 h to obtain a concentrated silanol prepolymer. The mixture in the reactor became a colorless, transparent, homogeneous phase. 1.13 g of hexamethyldisilazane was added dropwise to adjust the pH to 5.5. The mixture was allowed to stand and drain the lower layer of wastewater. The ethanol / methanol and water were then removed under vacuum at 75°C to obtain 1650 g of a pre-polymerized concentrated silicone resin. After cooling, 1650 g of ethanol was added to obtain a pre-polymerized concentrated silicone resin solution.

[0076] (b) 46 g of methyltrimethoxysilane and 33 g of isopropyl titanate were added to the pre-polymerized concentrated silicone resin solution obtained in step (a) for grafting, and the mixture was stirred and reacted at 85° C. for 4 h. After the reaction was completed, excess methanol and ethanol were evaporated to obtain 1640 g of the spherical silicone resin, and then 1640 g of ethanol was added to obtain a spherical silicone resin solution.

[0077] In the spherical silicone resin obtained in this example, R / Si=0.88.

[0078] Take 200g of the spherical silicone resin solution obtained above, add 3.1 parts by weight of methyltrimethoxysilane and 2.2g of tetrabutyl titanate, 0.1g of γ-glycidyloxypropyltrimethoxysilane, 1g of diethylene glycol monoethyl ether acetate, and 3g of butanol, stir and mix evenly, then fill with nitrogen and store in a sealed manner to obtain the organic silicon glass silicone resin.

[0079] Example 3

[0080] In this embodiment, an organosilicon glass silicone resin is provided, and a preparation method thereof comprises the following steps:

[0081] (a) 330 g of methyl orthosilicate, 2000 g of methyltriethoxysilane, 80 g of diethyldiethoxysilane, and 450 g of H2O were weighed and added to an enameled reactor, stirred and mixed, and then 0.18 g of concentrated hydrochloric acid was dropwise added. The mixture was then hydrolyzed with a stirrer and heated to 70°C for 4 h. The mixture was then refluxed and stirred at 120°C for 6 h to obtain a concentrated silanol prepolymer. The mixture in the reactor became a colorless, transparent, homogeneous phase. 0.82 g of hexamethyldisilazane was added dropwise to adjust the pH to 5.5. The mixture was allowed to stand and drain the lower layer of wastewater. Methanol, ethanol, and water were then removed under vacuum at 75°C to obtain 840 g of a pre-polymerized concentrated silicone resin. After cooling, 840 g of ethanol was added to obtain a pre-polymerized concentrated silicone resin solution.

[0082] (b) 23.6 g of methyltrimethoxysilane and 16.8 g of tetraethyl titanate were added to the pre-polymerized concentrated silicone resin solution obtained in step (a) for grafting, and the mixture was stirred and reacted at 85° C. for 4 h. After the reaction was completed, excess methanol and ethanol were evaporated to obtain 840 g of the spherical silicone resin, and then 840 g of ethanol was added to obtain a spherical silicone resin solution.

[0083] In the spherical silicone resin obtained in this example, R / Si=0.87.

[0084] Take 200g of the spherical silicone resin solution obtained above, add 2.8 parts by weight of methyltrimethoxysilane and 2.5g of tetrabutyl titanate, 2g of aminopropyltrimethoxysilane, 10g of diethylene glycol monoethyl ether acetate, and 3g of butanol, stir and mix evenly, then fill with nitrogen and store in a sealed manner to obtain the organic silicon glass silicone resin.

[0085] Example 4

[0086] In this embodiment, an organosilicon glass silicone resin is provided, and a preparation method thereof comprises the following steps:

[0087] (a) 450 g of methyl orthosilicate, 2100 g of methyltrimethoxysilane, 80 g of diethyldiethoxysilane, and 500 g of H2O were weighed and added to an enameled reactor, stirred and mixed, and then 0.22 g of concentrated hydrochloric acid was dropwise added. The mixture was then hydrolyzed with a stirrer and heated to 70°C for 4 h. The mixture was then refluxed and stirred at 120°C for 6 h to obtain a concentrated silanol prepolymer. The mixture in the reactor became a colorless, transparent, homogeneous phase. 0.9 g of hexamethyldisilazane was added dropwise to adjust the pH to 5.5. The mixture was allowed to stand and drain the lower layer of wastewater. Methanol, ethanol, and water were then removed under vacuum at 75°C to obtain 1360 g of a pre-polymerized concentrated silicone resin. After cooling, 1360 g of ethanol was added to obtain a pre-polymerized concentrated silicone resin solution.

[0088] (b) 38.7 g of methyltrimethoxysilane and 28 g of tetrabutyl titanate were added to the pre-polymerized concentrated silicone resin solution obtained in step (a) for grafting, and the mixture was stirred and reacted at 85° C. for 4 h. After the reaction was completed, excess methanol and ethanol were evaporated to obtain 1360 g of the spherical silicone resin, and then 1360 g of ethanol was added to obtain a spherical silicone resin solution.

[0089] In the spherical silicone resin obtained in this example, R / Si=0.9.

[0090] Take 200 g of the spherical silicone resin solution obtained above, add 3.5 g of methyltrimethoxysilane and 2.5 g of tetrabutyl titanate, 1 g of γ-aminoethylaminopropyltrimethoxysilane, 8 g of diethylene glycol monoethyl ether acetate, and 7 g of butanol, stir and mix evenly, then fill with nitrogen and store in a sealed manner to obtain the organic silicon glass silicone resin.

[0091] Example 5

[0092] In this embodiment, an organic silicone glass silicone resin is provided, and the preparation method comprises the following steps:

[0093] (a) Take tetraethyl orthosilicate 450 g, methyltrimethoxysilane 2600 g, diethyldiethoxysilane 80 g and H2O 680 g, add to the enamel reaction kettle and stir to mix, then add 0.27 g of concentrated hydrochloric acid dropwise, then start the stirrer and proceed with the hydrolysis, and the temperature is raised to 70°C for hydrolysis for 4 h. Then reflux stirring reaction at 120°C for 6 h to prepare concentrated silanol prepolymer, the material in the kettle becomes a colorless transparent homogeneous system, add 1.2 g of hexamethyldisilazane to adjust PH=5.5, let it stand and discard the lower layer of waste water, then vacuum out methanol and ethanol and water at 75°C to obtain 1340 g of pre-polymerized concentrated silicone resin, and then add 1340 g of ethanol to obtain a pre-polymerized concentrated silicone resin solution;

[0094] (b) To the pre-polymerized concentrated silicone resin solution obtained in step (a), add methyltrimethoxysilane 38.7 g and tetrabutyl titanate 28 g for grafting, and stir at 85°C for 4 h. After the reaction is completed, the excess methanol and ethanol solvents are evaporated to obtain 1330 g of the spherical silicone resin, and then add 1330 g of ethanol to obtain a spherical silicone resin solution.

[0095] In the spherical silicone resin obtained in this embodiment, R / Si=0.89.

[0096] Take 200 g of the spherical silicone resin solution obtained above, add 2.8 parts by weight of methyltrimethoxysilane, 1.9 g of tetrabutyl titanate, 1 g of γ-aminoethyl aminopropyl trimethoxysilane, 6 g of diethylene glycol monoethyl ether acetate, and 10 g of butanol, stir to mix uniformly, and then seal and store under nitrogen to obtain the organic silicone glass silicone resin.

[0097] Example 6

[0098] In this embodiment, an organic silicone glass silicone resin is provided, and the preparation method comprises the following steps:

[0099] (a) Take tetraethyl orthosilicate 450 g, methyltrimethoxysilane 2600 g, diethyldiethoxysilane 80 g and H2O 680 g, add to the enamel reaction kettle and stir to mix, then add 0.27 g of concentrated hydrochloric acid dropwise, then start the stirrer and proceed with the hydrolysis, and the temperature is raised to 70°C for hydrolysis for 4 h. Then reflux stirring reaction at 120°C for 6 h to prepare concentrated silanol prepolymer, the material in the kettle becomes a colorless transparent homogeneous system, add 1.2 g of hexamethyldisilazane to adjust PH=5.5, let it stand and discard the lower layer of waste water, then vacuum out methanol and ethanol and water at 75°C to obtain 1340 g of pre-polymerized concentrated silicone resin, and then add 1340 g of ethanol to obtain a pre-polymerized concentrated silicone resin solution;

[0100] (b) grafting methyltrimethoxysilane 21.8 g and tetrabutyl titanate 16.4 g to the prepolymer concentrated silicone resin solution obtained in step (a), stirring reaction at 70°C for 6 h, evaporating the excess methanol and ethanol after reaction, obtaining 820 g of the spherical silicone resin, then adding 820 g of ethanol to obtain a spherical silicone resin solution.

[0101] The R / Si of the spherical silicone resin obtained in this example is 0.878.

[0102] Take 200 g of the spherical silicone resin solution obtained above, add methyltrimethoxysilane 3 g and tetrabutyl titanate 2.3 g, γ-aminoethyl aminopropyl trimethoxysilane 1 g, diethylene glycol monoethyl ether acetate 5 g, butanol 5 g, stir and mix uniformly, then seal and store under nitrogen, to obtain the silicone glass silicone resin.

[0103] Example 7

[0104] In this example, a silicone glass silicone resin is provided, and the preparation method comprises the following steps:

[0105] (a) weigh tetraethyl orthosilicate 450 g, methyltriethoxysilane 2000 g, diethyldiethoxysilane 80 g and H2O 450 g, add to a porcelain reaction kettle and stir, then add 0.20 g of concentrated hydrochloric acid dropwise, then start the stirrer and hydrolyze, then raise the temperature to 75°C and hydrolyze for 1 h. Then reflux and stir at 150°C for 2 h to obtain a concentrated silanol prepolymer, the material in the kettle becomes a colorless transparent homogeneous system, add 0.88 g of hexamethyldisilazane to adjust the pH to 5.5, let stand and discard the lower layer of waste water, then remove ethanol and water under 75°C and -0.09 MPa vacuum to obtain 820 g of a prepolymer concentrated silicone resin, then add 820 g of ethanol after cooling to obtain a prepolymer concentrated silicone resin solution;

[0106] (b) grafting methyltrimethoxysilane 21.8 g and tetrabutyl titanate 16.4 g to the prepolymer concentrated silicone resin solution obtained in step (a), stirring reaction at 100°C for 2 h, evaporating the excess methanol and ethanol after reaction, obtaining 820 g of the spherical silicone resin, then adding 820 g of ethanol to obtain a spherical silicone resin solution.

[0107] The R / Si of the spherical silicone resin obtained in this example is 0.878.

[0108] Take 200 g of the spherical silicone resin solution obtained above, add methyltrimethoxysilane 3 g and tetrabutyl titanate 2.3 g, γ-aminoethyl aminopropyl trimethoxysilane 1 g, diethylene glycol monoethyl ether acetate 5 g, butanol 5 g, stir and mix uniformly, then seal and store under nitrogen, to obtain the silicone glass silicone resin.

[0109] Example 8

[0110] In this embodiment, an organosilicon glass silicone resin is provided, and a preparation method thereof comprises the following steps:

[0111] (a) 3180 g of ethyl orthosilicate, 2400 g of methyltriethoxysilane, 80 g of diethyldiethoxysilane, and 1300 g of H2O were weighed and added to an enameled reactor, stirred and mixed, and then 0.51 g of concentrated hydrochloric acid was added dropwise. The mixture was then hydrolyzed with a stirrer and heated to 70°C for 4 h. The mixture was then refluxed and stirred at 120°C for 6 h to obtain a concentrated silanol prepolymer. The mixture in the reactor became a colorless, transparent, homogeneous phase. 2.2 g of hexamethyldisilazane was added dropwise to adjust the pH to 5.5. The mixture was allowed to stand and drain the lower layer of wastewater. The ethanol and water were then removed under vacuum at 75°C at -0.09 MPa to obtain 2350 g of pre-polymerized concentrated silicone resin. After cooling, 2350 g of ethanol was added to obtain a pre-polymerized concentrated silicone resin solution.

[0112] (b) 65 g of methyltrimethoxysilane and 47 g of tetrabutyl titanate were added to the pre-polymerized concentrated silicone resin solution obtained in step (a) for grafting, and the mixture was stirred and reacted at 85° C. for 4 h. After the reaction was completed, excess methanol and ethanol were evaporated to obtain 2350 g of the spherical silicone resin, and then 2350 g of ethanol was added to obtain a spherical silicone resin solution.

[0113] In the spherical silicone resin obtained in this example, R / Si=0.5.

[0114] Take 200 g of the spherical silicone resin solution obtained above, add 2.8 g of methyltrimethoxysilane and 2.1 g of tetrabutyl titanate, 1 g of γ-aminoethylaminopropyltrimethoxysilane, 5 g of diethylene glycol monoethyl ether acetate, and 5 g of butanol, stir and mix evenly, then fill with nitrogen and store in a sealed manner to obtain the organic silicon glass silicone resin.

[0115] Example 9

[0116] In this embodiment, an organosilicon glass silicone resin is provided, and a preparation method thereof comprises the following steps:

[0117] (a) 500 g of ethyl orthosilicate, 4700 g of methyltriethoxysilane, 6400 g of diethyldiethoxysilane, and 2200 g of H2O were weighed and added to an enameled reactor, stirred and mixed, and then 0.88 g of concentrated hydrochloric acid was added dropwise. The mixture was then hydrolyzed with a stirrer and heated to 70°C for 4 h. The mixture was then refluxed and stirred at 120°C for 6 h to obtain a concentrated silanol prepolymer. The mixture in the reactor became a colorless, transparent, homogeneous phase. 3.89 g of hexamethyldisilazane was added dropwise to adjust the pH to 5.5. The mixture was allowed to stand and drain the lower layer of wastewater. The ethanol and water were then removed under vacuum at 75°C @ -0.09 MPa to obtain 7380 g of pre-polymerized concentrated silicone resin. After cooling, 7380 g of ethanol was added to obtain a pre-polymerized concentrated silicone resin solution.

[0118] (b) 205 g of methyltrimethoxysilane and 146 g of tetrabutyl titanate were added to the pre-polymerized concentrated silicone resin solution obtained in step (a) for grafting, and the mixture was stirred and reacted at 85° C. for 4 h. After the reaction was completed, excess methanol and ethanol were evaporated to obtain 7380 g of the spherical silicone resin, and then 7380 g of ethanol was added to obtain a spherical silicone resin solution.

[0119] In the spherical silicone resin obtained in this example, R / Si=1.5.

[0120] Take 200 g of the spherical silicone resin solution obtained above, add 2.8 g of methyltrimethoxysilane and 2.1 g of tetrabutyl titanate, 1 g of γ-aminoethylaminopropyltrimethoxysilane, 5 g of diethylene glycol monoethyl ether acetate, and 5 g of butanol, stir and mix evenly, then fill with nitrogen and store in a sealed manner to obtain the organic silicon glass silicone resin.

[0121] Comparative Example 1

[0122] This comparative example differs from Example 1 in that the spherical silicone resin is replaced with an equal amount of DY-MQ102N methyl MQ silicone resin (manufacturer: Shandong Dayi Chemical). Adaptively, this comparative example does not include steps (a) and (b) for synthesizing the spherical silicone resin.

[0123] The preparation method includes the following steps: taking 100 g of DY-MQ102N methyl MQ silicone resin (manufacturer: Shandong Dayi Chemical), adding 100 g of anhydrous ethanol, adding 2.8 g of methyltrimethoxysilane and 2.1 g of tetrabutyl titanate, 1 g of γ-aminoethylaminopropyltrimethoxysilane, 5 g of diethylene glycol monoethyl ether acetate, and 5 g of butanol, stirring and mixing evenly, filling with nitrogen and sealing for use, and testing.

[0124] The performance tests were performed on the organosilicon glass silicone resins provided in the examples and comparative examples. The test standards and performance test results are shown in Tables 1 and 2.

[0125] Table 1

[0126]

[0127] Table 2

[0128]

[0129]

[0130] As can be seen from Table 1 and Table 2, the organosilicon glass silicone resins provided in Examples 1-7 of the present invention all have high light transmittance (96%-99%), a specific gravity of 1.1±0.1 (g / cm3, 25±2°C), and a viscosity of 5mm 2 / s~20mm 2 / s, the dry time is 6-10 minutes, the excellent pencil hardness is above 6H, the abrasion resistance is less than 0.8% in haze value, the circle scratch adhesion is 1 level, and a thin coating on the surface of various substrates can achieve good protection.

[0131] Compared with Example 1, the light transmittance, the pencil hardness, the abrasion resistance and the adhesion of the organic silicon glass silicone resin provided in Example 8 are all decreased; the pencil hardness, the abrasion resistance and the adhesion of the organic silicon glass silicone resin provided in Example 9 are all decreased.

[0132] Compared with Example 1, the light transmittance, the pencil hardness, the abrasion resistance and the adhesion of the organic silicon glass silicone resin provided in Comparative Example 1 are all decreased.

[0133] The applicant declares that the organic silicon glass silicone resin, the preparation method and the application thereof are illustrated by the above examples, but the present application is not limited to the above examples, that is, the present application does not mean that it must rely on the above examples to be implemented. It should be understood by those skilled in the art that any improvement of the present application, equivalent replacement of each raw material of the product of the present application, addition of auxiliary ingredients, selection of specific modes, etc. all fall within the protection scope and the disclosed scope of the present application.

Claims

1. An organosilicon glass silicone resin, characterized in that: The raw materials for preparing the organosilicon glass silicone resin include the following components in parts by weight: 100 parts by weight of spherical silicone resin; 1 to 5 parts by weight of a cross-linking agent; 0.5-5 parts by weight of catalyst; 0.1 to 2 parts by weight of tackifier; 1-10 parts by weight of cellosolve; 1 to 10 parts by weight of a leveling agent; The spherical silicone resin has a structure shown in the following formula (I): [(R 2 SiO 3 / 2 ] a [R 1 2SiO 2 / 2 ] b [SiO 4 / 2 ] c [(R 3 2R 2 SiO 1 / 2 ] d formula (I) Among them, R 1 =C2H5、R 2 =CH3、R 3 =CH3O or C2H5O; a, b, c, d represent molar ratios and satisfy the following conditions: a is 0.65 to 0.9, b is 0.01 to 0.05, c is 0.1 to 0.35, d is 0.001 to 0.2, and a+b+c=1; The molar ratio of R to Si is 0.6 to 1.4, and R is R 1 、R 2 and R 3 The group represented.

2. The organosilicon glass silicone resin according to claim 1, characterized in that The spherical silicone resin is prepared by the following method: (a) mixing an alkyl orthosilicate, an alkyltrialkoxysilane, a diethyldialkoxysilane and water, then adding an acid catalyst, heating, and hydrolyzing the mixture under stirring, followed by reacting the mixture under reflux and stirring, then adding a pH adjuster, allowing the mixture to stand, draining the lower layer of wastewater, and then removing the alcohol and water under vacuum to obtain a prepolymerized concentrated silicone resin, and then adding a reactive diluent to obtain a prepolymerized concentrated silicone resin solution; (b) adding alkyltrialkoxysilane and titanium catalyst to the pre-polymerized concentrated silicone resin solution obtained in step (a), reacting, then distilling off methanol, ethanol and reactive diluent to obtain the spherical silicone resin, and then adding reactive diluent to obtain a spherical silicone resin solution.

3. The organosilicon glass silicone resin according to claim 2, characterized in that: The alkyl orthosilicate includes methyl orthosilicate and / or ethyl orthosilicate.

4. The organosilicon glass silicone resin according to claim 2, characterized in that: The alkyltrialkoxysilane in step (a) and step (b) each independently comprises methyltrimethoxysilane and / or methyltriethoxysilane.

5. The organosilicon glass silicone resin according to claim 2, characterized in that: The diethyldialkoxysilane in step (a) includes diethyldiethoxysilane.

6. The organosilicon glass silicone resin according to claim 2, characterized in that: The ratio of the total molar number of alkoxy groups in the alkyl orthosilicate, alkyltrialkoxysilane and diethyldialkoxysilane to the molar number of water is 1:(0.4-0.8).

7. The organosilicon glass silicone resin according to claim 2, characterized in that: The molar ratio of the alkyl orthosilicate, alkyltrialkoxysilane and diethyldialkoxysilane is (0.1-0.35):(0.65-0.9):(0.01-0.05).

8. The organosilicon glass silicone resin according to claim 2, characterized in that: The acid catalyst includes any one of hydrochloric acid, acetic acid, formic acid, boric acid, nitric acid, sulfuric acid or trifluoromethanesulfonic acid, or a combination of at least two thereof.

9. The organosilicon glass silicone resin according to claim 2, characterized in that: The amount of the acid catalyst added is such that the pH value of the system is 3-4.

10. The organosilicon glass silicone resin according to claim 2, characterized in that: The heating in step (a) is to be raised to 40-75°C.

11. The organosilicon glass silicone resin according to claim 2, characterized in that: The hydrolysis time in step (a) is 1 to 8 hours.

12. The organosilicon glass silicone resin according to claim 2, characterized in that: The reaction temperature in step (a) is 75-150° C., and the reaction time is 2-8 hours.

13. The organosilicon glass silicone resin according to claim 2, characterized in that: The pH adjuster includes hexamethyldisilazane and / or a base.

14. The organosilicon glass silicone resin according to claim 2, characterized in that: The amount of the pH regulator added is such that the pH value of the system is 5-6.

15. The organosilicon glass silicone resin according to claim 2, characterized in that: The temperature for removing alcohol and water in step (a) is 40-120°C.

16. The organosilicon glass silicone resin according to claim 2, characterized in that: The pre-polymerized concentrated silicone resin has a structure shown in the following formula (II): [R 2 SiO 3 / 2 ] a [(R 1 2SiO 2 / 2 ] b [SiO 4 / 2 ] c [HO 1 / 2 ] d Among them, R 1 =C2H5、R 2 =CH3; a, b, c, d represent molar ratios and satisfy the following conditions: a is 0.65 to 0.9, b is 0.01 to 0.05, c is 0.1 to 0.35, d is 0.001 to 0.2, and a+b+c=1; The molar ratio of R to Si is 0.6 to 1.4, and R is R 1 and R 2 The group represented.

17. The organosilicon glass silicone resin according to claim 2, characterized in that: The active diluent added in step (a) and step (b) includes any one of ethyl acetate, butyl acetate, aromatic hydrocarbon solvents, ketone solvents or alcohol solvents, or a combination of at least two thereof.

18. The organosilicon glass silicone resin according to claim 2, characterized in that: The mass ratio of the pre-polymerized concentrated silicone resin to the reactive diluent in step (a) is 1:(0.8-1.2).

19. The organosilicon glass silicone resin according to claim 2, characterized in that: In step (b), the amount of the alkyltrialkoxysilane added is 0.5 to 5% by weight of the pre-polymerized concentrated silicone resin.

20. The organosilicon glass silicone resin according to claim 2, characterized in that: The titanium catalyst includes any one or a combination of at least two of tetrabutyl titanate, isopropyl titanate, tetraethyl titanate, organic alkoxy titanate chelate or organic titanium chelate.

21. The organosilicon glass silicone resin according to claim 20, characterized in that The organic titanium chelate is diisopropoxybis(ethyl acetoacetate)titanium.

22. The organosilicon glass silicone resin according to claim 2, characterized in that: In step (b), the amount of the titanium catalyst added is 1 to 5% by weight of the pre-polymerized concentrated silicone resin.

23. The organosilicon glass silicone resin according to claim 2, characterized in that: The reaction temperature in step (b) is 70-100° C., and the reaction time is 2-6 hours.

24. The organosilicon glass silicone resin according to claim 2, characterized in that In step (b), the mass ratio of the spherical silicone resin to the reactive diluent is 1:(0.6-1.5).

25. The organosilicon glass silicone resin according to claim 1, characterized in that The crosslinking agent includes any one of methyltrimethoxysilane, vinyltrimethoxysilane, methyltriethoxysilane, vinyltriethoxysilane, tetramethoxysilane or tetraethoxysilane, or a combination of at least two thereof.

26. The organosilicon glass silicone resin according to claim 1, characterized in that The catalyst includes any one of tetrabutyl titanate, isopropyl titanate, tetraethyl titanate or titanate chelate, or a combination of at least two of the above.

27. The organosilicon glass silicone resin according to claim 1, characterized in that The adhesion promoter includes any one of γ-glycidoxypropyltrimethoxysilane, aminopropyltrimethoxysilane, aminopropyltriethoxysilane or γ-aminoethylaminopropyltrimethoxysilane, or a combination of at least two thereof.

28. The organosilicon glass silicone resin according to claim 1, characterized in that The cellosolve includes diethylene glycol monoethyl ether acetate.

29. The organosilicon glass silicone resin according to claim 1, characterized in that The leveling agent includes butanol.

30. A method for preparing an organosilicon glass silicone resin according to any one of claims 1 to 29, characterized in that: The preparation method comprises the following steps: The spherical silicone resin in a prescribed amount is mixed with a cross-linking agent and a catalyst, and then a tackifier, a cellosolve and a leveling agent are added and mixed to obtain the organosilicon glass silicone resin.

31. The method for preparing organosilicon glass silicone resin according to claim 30, characterized in that: The spherical silicone resin is added in the form of a spherical silicone resin solution.

32. The method for preparing organosilicon glass silicone resin according to claim 30, characterized in that: The spherical silicone resin solution comprises spherical silicone resin and a reactive diluent.

33. The method for preparing organosilicon glass silicone resin according to claim 30, characterized in that: In the spherical silicone resin solution, based on 100 parts by weight of the spherical silicone resin, the weight of the reactive diluent is 20 to 300 parts by weight.

34. Use of the organosilicon glass silicone resin according to any one of claims 1 to 29 in glass lenses.

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